US5849835A - Polyisocyanate cured ultradurable glossy coating compositions - Google Patents
Polyisocyanate cured ultradurable glossy coating compositions Download PDFInfo
- Publication number
- US5849835A US5849835A US08/574,825 US57482595A US5849835A US 5849835 A US5849835 A US 5849835A US 57482595 A US57482595 A US 57482595A US 5849835 A US5849835 A US 5849835A
- Authority
- US
- United States
- Prior art keywords
- meth
- acrylate
- composition
- hydroxyl
- cyclohexyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
Definitions
- the present invention relates to polyisocyanate-curable, film-forming compositions, and processes for preparing multi-layered coated articles comprising a pigmented or colored base coat and a clear topcoat.
- Color-plus-clear coating systems have become conventional as original finishes for automobiles. These systems typically involve the application of a pigmented base coat to a substrate. This is followed by the application of a clear topcoat over the base coat. These color-plus-clear systems have outstanding gloss and distinctness of image, most of which is provided by the clear topcoat.
- the clear topcoat in this color-plus-clear system In addition to having a high gloss, it is often desirable for the clear topcoat in this color-plus-clear system to be ultradurable and acid etch resistant.
- ultradurable refers to the ability of the topcoat to retain a large percentage of its original gloss when exposed to environmental conditions such as rain, sun, heat, freezing temperatures, and the like.
- Coating systems which are known to be durable are described in U.S. Pat. No. 4,565,730. That Patent describes coating compositions which contain as binders a combination of two specific hydroxyl-containing acrylate resins and an aliphatic and/or cycloaliphatic polyisocyanate or a mixture of such polyisocyanates.
- the hydroxyl number of the first of the two specific acrylic polymers ranges from between 80 to 180 and is present in an amount ranging from between 50 to 90% by weight, based on total acrylic polymers.
- the hydroxyl number of the second of the two specific acrylic polymers ranges from between 40 to 120 and is present in an amount ranging from between 10 to 50% by weight, based on total acrylic polymers.
- Another object of this invention is to provide a color-plus-clear coating system which includes a novel clear, high gloss topcoat which is ultradurable and resists acid etching.
- a curable film-forming composition which includes: (a) a hydroxyl-containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent.
- the hydroxyl-containing acrylic solution polymer is present in an amount ranging from between about 60 to about 90 weight percent; and, the polyisocyanate crosslinking agent is present in an amount ranging from between about 10 to about 40 weight percent.
- the acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of acrylic acid or methacrylic acid (hereinafter referred to as "(meth)acrylic acid") having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component.
- the cycloaliphatic and/or aromatic ester component is typically employed in an amount ranging from between about 45 to about 95 weight percent.
- the hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60. It has been discovered that the coating compositions made in accordance with the present invention are not only ultradurable, but also acid etch resistant.
- This invention also provides a process for applying a composite coating onto a substrate.
- This process includes: (a) applying a film-forming base coat onto a substrate, (b) at least partially curing the base coat, and (c) applying a clear, film-forming top coat over the at least partially cured base coat.
- the clear top coat being applied over the base coat includes the curable, film-forming composition described above.
- the present invention pertains to the development of a novel, crosslinkable film-forming composition which has a high gloss, is ultradurable and resists acid etching.
- This film-forming composition includes: (a) a hydroxyl-containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent.
- acrylic solution polymer means that the acrylic polymer is prepared by solution polymerization techniques while in the presence of suitable initiators such as organic peroxides or azo compounds (e.g., benzoyl peroxide or 2,2'-azobis(2-methylbutanenitrile)).
- suitable initiators such as organic peroxides or azo compounds (e.g., benzoyl peroxide or 2,2'-azobis(2-methylbutanenitrile)).
- This polymerization can be carried out in an organic solvent in a conventional manner in which the monomers and polymers produced are soluble.
- the acrylic solution polymer is typically present in the film-forming composition in an amount ranging from between about 60 to about 90 weight percent, and preferably, from between about 70 to about 85 weight percent. These weight percentages are based upon the total resin solids weight of a hydroxyl-containing acrylic solution polymer in the film-forming composition.
- the polyisocyanate crosslinking agent is typically present in the film-forming composition in an amount ranging from between about 10 to about 40 weight percent, and preferably, from between about 15 to about 30 weight percent. These weight percentages are based upon the total resin solids weight of an polyisocyanate crosslinking agent in the film-forming composition.
- the acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of (meth)acrylic acid having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component.
- the hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60.
- the cycloaliphatic or aromatic ester component is typically employed in an amount ranging from between about 45 to about 95 weight percent, and preferably, from between about 60 to about 90 weight percent. These weight percentages are based upon total weight of monomers used in preparing the acrylic solution polymer.
- the cycloaliphatic or aromatic ester component has at least 6 carbon atoms in the cycloaliphatic or aromatic group, typically, it has from between 6 to 12 carbon atoms.
- examples of such compounds which can be used when practicing this invention include: benzyl methacrylate, phenyl methacrylate, t-butyl-cyclohexyl methacrylate and cyclohexyl methacrylate or mixtures thereof. Cyclohexyl methacrylate is preferred.
- the hydroxyl functional acrylic monomer component is typically employed in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60.
- the amount of the hydroxyl functional acrylic monomer component employed is such that the acrylic solution polymer's hydroxyl number is in the range from between about 25 to about 55, and more preferably, from between about 30 to about 55. Any suitable hydroxyl functional monomer, or combination thereof, can be used when practicing this invention.
- Suitable monomers include: hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2- and 4-hydroxybutyl acrylate, and 2- and 4-hydroxybutyl methacrylate or mixtures thereof.
- the hydroxyl functional monomers most preferred for providing acid etch resistance are 2-hydroxybutyl acrylate and 2-hydroxypropyl acrylate.
- the acrylic solution polymer may further include up to 45 weight percent of a monomer(s) such as vinyl aromatic compounds and alkyl acrylates and methacrylates which contain from 1 to 8 carbon atoms in the alkyl group. This weight percent is based upon total weight of monomers used in preparing the acrylic solution polymer.
- Suitable vinyl aromatic compounds which can be used include: styrene and vinyl toluene. Styrene is preferred.
- Suitable alkyl acrylates and methacrylates which can be used include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. A mixture of n-butyl acrylate and methyl methacrylate is preferred.
- the acrylic solution polymer typically has a number average molecular weight ranging from between about 1,000 to about 30,000, and preferably, from -between about 1,500 to 20,000. These molecular weights are determined by gel permeation chromatography using polystyrene as standard.
- the crosslinking agent can be any one or more polyisocyanate(s) which can be used in organic solvents.
- polyisocyanates which can be used when practicing this invention include: toluene diisocyanates, isocyanurates of toluene diisocyanate, diphenylmethane 4,4-'diisocyanate, isocyanurates of 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, p-phenylene diisocyanate, triphenylmethane 4,4',4"-triiocyanate, metaxylene diisocyanate and polyisocyanates, 1,6-hexamethylene diisocyanate, isocyanurates of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, isocyanurates of isophorone diisocyanate, methylene bis-4,4'-isocyanatocyclohexane, and 1,3-bis
- polyisocyanates preferred use is made of 1,6-hexamethylene diisocyanate and isophorone diisocyanate, isocyanurate- and/or biuret-containing polyisocyanates which are derived from the latter and which preferably contain more than 2 isocyanate groups in the molecule.
- the polyisocyanates used when practicing this invention can be both in free and in blocked form. If the polyisocyanate being employed is in a blocked form, any blocking agent can be used, provided that the agent has a sufficiently low deblocking temperature.
- Groups suitable for use as the blocker portion of a blocked isocyanate are also well-known in the art.
- suitable groups include: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols and amines.
- oximes e.g., acetone oxime, methyl ethyl ketoxime, methyl amyl ketoxime, diisobutyl ketoxime, formaldehyde oxime
- oximes e.g., acetone oxime, methyl ethyl ketoxime, methyl amyl ketoxime, diisobutyl ketoxime, formaldehyde oxime
- the film-forming composition contains a catalyst to accelerate the cure of the polyisocyanate and other -crosslinkable groups.
- a catalyst to accelerate the cure of the polyisocyanate and other -crosslinkable groups.
- useful catalysts include: metal acetonyl acetates, quaternary ammonium salts, zinc N-ethyl-N-phenyl dithiocarbamate, pentamethyl-diethylenetriamine benzoate, cyclohexylamine acetate, n,n-dimethyl cyclohexylamine acetate, ketimines, N-methyl morpholine, tin octoate, stannic chloride, butyl tin trichloride, dibutyl tin diacetate, dibutyl tin dilaurate, bis(2-ethylhexyl) tin oxide, 1,3-diacetoxy tetrabutyl stannoxate, dibutyl
- the catalyst is usually present in an amount ranging from between about 0.1 to about 5 weight percent, and preferably, from between about 0.5 to about 2 weight percent. These weight percentages are based upon the total weight of the resin solids in the coating composition.
- optional ingredients such as plasticizers, flow controllers, anti-oxidants, UV light absorbers and other similar additives known in the art, can also be included in the coating composition. If employed, the cumulative weight of these optional ingredients are typically present at up to about 25 weight percent. This weight percentage is based upon the total weight of the resin solids in the coating composition.
- the crosslinkable film-forming coating composition of the present invention can be used as the clear top coat layer in a "color-plus-clear" coating system.
- the base coat in a color-plus-clear system encompassed by the present invention can be any of the compositions useful in coatings applications, particularly those in automotive and general industrial applications.
- the film-forming composition of the base coat typically includes a resinous binder and a pigment. Examples of particularly useful resinous binders include acrylic polymers, polyesters (including alkyds) and polyurethanes.
- the base coat compositions may be solvent-borne or water-borne.
- water-borne base coats in a color-plus-clear system encompassed by the present invention are disclosed in U.S. Pat. No. 4,403,003.
- water-borne polyurethanes such as those disclosed in U.S. Pat. No. 4,147,679, can also be used as the resinous binder in the base coat to prepare a coating-plus-clear system which is encompassed by the present invention.
- water-borne coatings such as those described in U.S. Pat. No. 5,071,904, can also be used as a base coat.
- Base coats also often contain pigments in order to give them the desired color.
- base coat compositions containing metallic flake pigmentation are often used in the production of so-called "glamour metallic" finishes. These types of finishes are mainly used in the automotive industry. Examples of metallic flakes which can be used in a base coat of a color-plus-clear system encompassed by this invention include: aluminum flake, copper bronze flake and metal oxide coated mica.
- the base coat compositions may also contain non-metallic color pigments conventionally used in surface coatings.
- non-metallic color pigments include: inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green.
- non-metallic pigments are typically incorporated into the base coat composition in an amount ranging from between about 1 to about 80 percent by weight based on the total weight of coating solids.
- metallic pigments are typically employed in an amount ranging from between about 0.5 to 25 percent by weight based on the total weight of coating solids.
- the base coat composition may contain additional materials well known in the art of formulated surface coatings.
- additional materials include: surfactants, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts, and other customary auxiliaries. If employed, the cumulative weight of these materials can constitute up to 40 percent by weight of the total weight of the coating composition.
- the base coat compositions of a color-plus-clear system encompassed by the present invention can be applied to various substrates such as metals, plastics, wood, glass, woven fibers, non-woven fibers, foams, or a combination thereof. They are, however, particularly useful when applied over metals and elastomeric substrates that are found on motor vehicles.
- the base coat compositions can be applied over such substrates by conventional means including brushing, dipping, flow coating, spraying and the like. Most often, the base coat composition is applied by spraying. Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used.
- the base coat thickness ranges from between about 0.01 to about 10 mils, and preferably, from between about 0.05 to about 5 mils, and even more preferably, from between about 0.1 to about 2 mils.
- a film is formed on the surface of the substrate by driving solvent out of the base coat by heating or by an air drying period.
- the drying period is only for that time which is sufficient to ensure that the clear top coat can be applied over the base coat without the top coat dissolving the base coat.
- Suitable drying conditions will depend, in part, upon the particular base coat composition, the ambient humidity, and the like. In general, a drying time of from about 1 to about 5 minutes, at a temperature of about 68°-250° F. (20°-121° C.), will be adequate to ensure that mixing or "soak-in" of the two coats is minimized. At the same time, however, the base coat film is adequately wetted by the clear top coat composition so that satisfactory intercoat adhesion is obtained.
- More than one base coat and/or top coat may be applied to develop the optimum appearance of a color-plus-clear system encompassed by the present invention.
- the previously applied coat is flashed (i.e., exposed to ambient conditions for about 1 to 20 minutes) between coats.
- the clear top coat composition can be applied over the base coat film by any conventional coating technique.
- conventional techniques include: brushing, dipping, flow coating, spraying and the like. Most often, the top coat is applied by spraying.
- Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used.
- the coated substrate is heated to cure the coating layers.
- solvents are driven off and the film-forming materials of the clear coat and the base coat are each crosslinked.
- the heating or curing operation is usually carried out at a temperature of about 160°-350° F. (71°-177° C.). If needed, however, lower or higher temperatures may be used as necessary to activate crosslinking mechanisms.
- the thickness of the clear coat layer usually ranges from between about 0.1 to about 10 mils, preferably, from between about 0.5 to about 7 mils, and even more preferably, from between about 1 to about 5 mils.
- the initial charge was heated in a reaction vessel with agitation to reflux temperature (138° C.).
- reflux Feeds A and B were initiated simultaneously and continued in a substantially continuous manner over a period of 3 hours while maintaining the reaction mixture at reflux temperature.
- the reaction mixture was held for 2 hours at reflux temperature to complete the polymerization.
- the reaction mixture was cooled and filtered.
- the resultant acrylic resin had a total solids content of 61.0 percent determined at 110° C. for one hour and number average molecular weight (Mn) of 2074 as determined by gel permeation chromatography (GPC) using polystyrene as standard.
- Mn number average molecular weight
- the resin had a Gardner-Holdt viscosity measured at 25° C. of P+.
- the free radical addition polymers containing various amount of cyclohexyl methacrylate and hydroxyl functional monomers were prepared similar to Example 1 and their composition, solvent, solids content, Gardner-Holdt viscosity and number average molecular weight are tabulated in Table I.
- a hydroxy functional polymer was prepared in accordance with Example II.1 of U.S. Pat. No. 4,565,730. That polymer was prepared as follows:
- the initial charge was heated in a reaction vessel with agitation to reflux temperature (163° C.). At reflux, Feeds A and B were initiated simultaneously and continued in a substantially continuous manner.
- the monomer mixture (Feed A) was added over a period of 4 hours and the initiator solution (Feed B) was added over 4.5 hours while maintaining the reaction mixture at reflux temperature.
- the reaction mixture was held for 1 hour at reflux temperature to complete the polymerization.
- the reaction mixture was cooled and filtered.
- the resultant acrylic resin had a total solids content of 61.9 percent determined at 110° C. for one hour and number average molecular weight of 2092 as determined by gel permeation chromatography using polystyrene as a standard.
- the resin had a Gardner-Holdt viscosity measured at 25° C. of I-.
- a hydroxy functional polymer was prepared in accordance with Example III.1 of U.S. Pat. No. 4,565,730. That polymer was prepared as follows:
- the initial charge was heated in a reaction vessel with agitation to reflux temperature (131° C.). At reflux, Feeds A and B were initiated simultaneously and continued in a substantially continuous manner.
- the monomer mixture (Feed A) was added over a period of 4 hours and the initiator solution (Feed B) was added over 4.5 hours while maintaining the reaction mixture at reflux temperature.
- the reaction mixture was held for 1 hour at reflux temperature to complete the polymerization.
- the reaction mixture was cooled and filtered.
- the resultant acrylic resin had a total solids content of 60.8 percent determined at 110° C. for one hour and number average molecular weight of 12787 as determined by gel permeation chromatography using polystyrene as a standard.
- the resin had a Gardner-Holdt viscosity measured at 25° C. of Z7-.
- a pigmented black base coating composition was used which is a high-solids polyester base coating composition available from PPG Industries, Inc. as POLYCRON® III base coat.
- a clear film forming composition was formulated from the following ingredients:
- Comparative clear coating compositions containing DESMODUR® BL 3175A and hydroxyl functional polymers were formulated similar to Examples 16-27 using Comparative Examples 13-14 and commercially available fluorinated polyols. Their compositions in grams of resin solids are tabulated in Table III.
- the base coating composition prepared according to Example 15 was air-atomized spray applied to pretreated aluminum panels at room temperature to attain a dry film thickness of 0.8 to 1.2 mils. After a 10 minute flash, the panels were then baked for 10 minutes at 350° F. (177° C.). The panels were allowed to cool room temperature and the prepared clear coating compositions were applied to the base coating.
- the clear coatings of Examples 16 to 27 and Comparative Examples 28 to 32 were applied in four successive coats at room temperature with film ranges from 1.8 to 2.2 mils. Each panel was given a 10 minute flash at room temperature, 10 minute "force" flash at 150° F. (66° C.), and then baked for 30 minutes at 285° F. (141° C.).
- the films were then evaluated for durability and acid etch resistance.
- the durability tests were done using Xenon arc Weather-Ometer with quartz/borosilicate filter combination from 340 nm. The cycle was: 40 minutes light; 20 minutes light with specimen spray; 60 minutes light; 60 minutes dark cycle with both specimen and rack spray. The results after 2000 hours exposure are tabulated in Table IV.
- the acid etch resistance of the films were evaluated via a 3-cycle sulfurous acid spray test.
- the acid solution with pH of 2 was prepared by adding 12 grains of H 2 SO 3 to 350 grams of deionized water.
- the test consists of misting 3" ⁇ 5" panel sections with the acid solution to completely cover the panels densely with droplets and then placing the panels in a 120° F. (49° C.) oven for 20 minutes. This constitutes one cycle. The procedure is then repeated two times. The panels are then washed with soap and water and towel dried for evaluation.
- the acid etch results are reported in Table IV.
Abstract
A curable, film-forming composition is provided which includes: (a) a hydroxyl-containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent. The hydroxyl-containing acrylic solution polymer is present in an amount ranging from between about 60 to about 90 weight percent; and, the polyisocyanate crosslinking agent is present in an amount ranging from between about 10 to about 40 weight percent. The acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of (meth)acrylic acid having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component. The hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60. This invention also provides a color-plus-clear coating system. This system includes: (a) applying a film-forming base coat onto a substrate, and (b) applying a clear, film-forming topcoat over the base coat. The clear topcoat includes the curable, film-forming composition described above.
Description
The present invention relates to polyisocyanate-curable, film-forming compositions, and processes for preparing multi-layered coated articles comprising a pigmented or colored base coat and a clear topcoat.
Color-plus-clear coating systems have become conventional as original finishes for automobiles. These systems typically involve the application of a pigmented base coat to a substrate. This is followed by the application of a clear topcoat over the base coat. These color-plus-clear systems have outstanding gloss and distinctness of image, most of which is provided by the clear topcoat.
In addition to having a high gloss, it is often desirable for the clear topcoat in this color-plus-clear system to be ultradurable and acid etch resistant. As used herein, the term "ultradurable" refers to the ability of the topcoat to retain a large percentage of its original gloss when exposed to environmental conditions such as rain, sun, heat, freezing temperatures, and the like.
Coating systems which are known to be durable are described in U.S. Pat. No. 4,565,730. That Patent describes coating compositions which contain as binders a combination of two specific hydroxyl-containing acrylate resins and an aliphatic and/or cycloaliphatic polyisocyanate or a mixture of such polyisocyanates. The hydroxyl number of the first of the two specific acrylic polymers ranges from between 80 to 180 and is present in an amount ranging from between 50 to 90% by weight, based on total acrylic polymers. The hydroxyl number of the second of the two specific acrylic polymers ranges from between 40 to 120 and is present in an amount ranging from between 10 to 50% by weight, based on total acrylic polymers.
In the past, it was believed that, in order to make coatings ultradurable, it is necessary for the polymers to contain fluoroine. However, while coatings based on polyvinylidene difluroide are ultradurable, they do not have a high gloss.
Notwithstanding the above, the fluoropolymers described in U.S. Pat. No. 4,345,057. have a high gloss and are ultradurable. The fluoropolymers described in that Patent are based on chlorotrifluoroethylene, vinyl ethers and hydroxy functionality to facilitate curing with polyisocyanates. However, these fluoropolymers are very expensive. Moreover, there is special equipment required to work with these gaseous monomers.
Processes for applying a double-layered covering lacquer on the surface of a substrate are disclosed in International (PCT) Application WO 94/22969. This PCT Application discloses processes which use a transparent covering lacquer containing a hydroxyl group-containing polyacrylate resin produced by polymerizing: (a) 10 to 51% by weight, preferably 25 to 41% by weight, of 4-hydroxy-n-butylacrylate or 4-hydroxy-n-butylmethacrylate, or a mixture thereof, and (b) 28 to 85% by weight, preferably 40 to 70% by weight, of an aliphatic or cycloaliphatic ester of methacrylic acid with at least 4 carbon atoms in the alcohol radical which is different from (a), above. The resulting polyacrylate resin has a hydroxyl number ranging from between 60 to 200, preferably, from between 100 to 160.
Commonly-owned U.S. Pat. No. 5,445,850 is entitled "Aminoplast Cured Acid Etch Resistant Coating with Good Durability." That Patent discloses coating compositions and their use in color-plus-clear coating systems. These coating compositions include acrylic polymers prepared with high levels of cycloaliphatic or aromatic ester of acrylic and methacrylic acid and hydroxypropyl- or hydroxybutyl acrylates and methacrylates and aminoplast crosslinking agents.
It is one object of this invention to provide a novel high gloss clear coating composition which is ultradurable and resists acid etching.
Another object of this invention is to provide a color-plus-clear coating system which includes a novel clear, high gloss topcoat which is ultradurable and resists acid etching.
These and other objects are achieved by the discovery of novel coating compositions which can be used as a clear top coat of a color-plus-clear coating system. In accordance with the present invention, a curable film-forming composition is provided which includes: (a) a hydroxyl-containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent. The hydroxyl-containing acrylic solution polymer is present in an amount ranging from between about 60 to about 90 weight percent; and, the polyisocyanate crosslinking agent is present in an amount ranging from between about 10 to about 40 weight percent. These weight percentages are based upon the total resin solids of the hydroxyl-containing acrylic solution polymer and the polyisocyanate crosslinking agent, respectively, in the film forming composition.
The acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of acrylic acid or methacrylic acid (hereinafter referred to as "(meth)acrylic acid") having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component. The cycloaliphatic and/or aromatic ester component is typically employed in an amount ranging from between about 45 to about 95 weight percent. Moreover, the hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60. It has been discovered that the coating compositions made in accordance with the present invention are not only ultradurable, but also acid etch resistant.
This invention also provides a process for applying a composite coating onto a substrate. This process includes: (a) applying a film-forming base coat onto a substrate, (b) at least partially curing the base coat, and (c) applying a clear, film-forming top coat over the at least partially cured base coat. The clear top coat being applied over the base coat includes the curable, film-forming composition described above.
These and other aspects and advantages of this invention will become apparent to those skilled in the art upon reading the following Detailed Description.
The present invention pertains to the development of a novel, crosslinkable film-forming composition which has a high gloss, is ultradurable and resists acid etching. This film-forming composition includes: (a) a hydroxyl-containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent.
As used herein, the term "acrylic solution polymer" means that the acrylic polymer is prepared by solution polymerization techniques while in the presence of suitable initiators such as organic peroxides or azo compounds (e.g., benzoyl peroxide or 2,2'-azobis(2-methylbutanenitrile)). This polymerization can be carried out in an organic solvent in a conventional manner in which the monomers and polymers produced are soluble.
When practicing this invention, the acrylic solution polymer is typically present in the film-forming composition in an amount ranging from between about 60 to about 90 weight percent, and preferably, from between about 70 to about 85 weight percent. These weight percentages are based upon the total resin solids weight of a hydroxyl-containing acrylic solution polymer in the film-forming composition. On the other hand, the polyisocyanate crosslinking agent is typically present in the film-forming composition in an amount ranging from between about 10 to about 40 weight percent, and preferably, from between about 15 to about 30 weight percent. These weight percentages are based upon the total resin solids weight of an polyisocyanate crosslinking agent in the film-forming composition.
The acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of (meth)acrylic acid having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component. The hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60. The cycloaliphatic or aromatic ester component is typically employed in an amount ranging from between about 45 to about 95 weight percent, and preferably, from between about 60 to about 90 weight percent. These weight percentages are based upon total weight of monomers used in preparing the acrylic solution polymer. Moreover, although the cycloaliphatic or aromatic ester component has at least 6 carbon atoms in the cycloaliphatic or aromatic group, typically, it has from between 6 to 12 carbon atoms. Examples of such compounds which can be used when practicing this invention include: benzyl methacrylate, phenyl methacrylate, t-butyl-cyclohexyl methacrylate and cyclohexyl methacrylate or mixtures thereof. Cyclohexyl methacrylate is preferred.
On the other hand, the hydroxyl functional acrylic monomer component is typically employed in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60. Preferably, the amount of the hydroxyl functional acrylic monomer component employed is such that the acrylic solution polymer's hydroxyl number is in the range from between about 25 to about 55, and more preferably, from between about 30 to about 55. Any suitable hydroxyl functional monomer, or combination thereof, can be used when practicing this invention. Examples of such suitable monomers include: hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2- and 4-hydroxybutyl acrylate, and 2- and 4-hydroxybutyl methacrylate or mixtures thereof. The hydroxyl functional monomers most preferred for providing acid etch resistance are 2-hydroxybutyl acrylate and 2-hydroxypropyl acrylate.
The acrylic solution polymer may further include up to 45 weight percent of a monomer(s) such as vinyl aromatic compounds and alkyl acrylates and methacrylates which contain from 1 to 8 carbon atoms in the alkyl group. This weight percent is based upon total weight of monomers used in preparing the acrylic solution polymer. Suitable vinyl aromatic compounds which can be used include: styrene and vinyl toluene. Styrene is preferred. Suitable alkyl acrylates and methacrylates which can be used include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. A mixture of n-butyl acrylate and methyl methacrylate is preferred.
The acrylic solution polymer typically has a number average molecular weight ranging from between about 1,000 to about 30,000, and preferably, from -between about 1,500 to 20,000. These molecular weights are determined by gel permeation chromatography using polystyrene as standard.
The crosslinking agent can be any one or more polyisocyanate(s) which can be used in organic solvents. Examples of polyisocyanates which can be used when practicing this invention include: toluene diisocyanates, isocyanurates of toluene diisocyanate, diphenylmethane 4,4-'diisocyanate, isocyanurates of 4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, p-phenylene diisocyanate, triphenylmethane 4,4',4"-triiocyanate, metaxylene diisocyanate and polyisocyanates, 1,6-hexamethylene diisocyanate, isocyanurates of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, isocyanurates of isophorone diisocyanate, methylene bis-4,4'-isocyanatocyclohexane, and 1,3-bis-(2-isocyanate propyl-2-)benzene (TMXDI), as well as adducts of these polyisocyanates on polyols, especially low molecular weight polyols (e.g., trimethylol propane) and isocyanurate group-containing and/or biuret group-containing polyisocyanates derived therefrom. As polyisocyanates, preferred use is made of 1,6-hexamethylene diisocyanate and isophorone diisocyanate, isocyanurate- and/or biuret-containing polyisocyanates which are derived from the latter and which preferably contain more than 2 isocyanate groups in the molecule.
The polyisocyanates used when practicing this invention can be both in free and in blocked form. If the polyisocyanate being employed is in a blocked form, any blocking agent can be used, provided that the agent has a sufficiently low deblocking temperature.
Groups suitable for use as the blocker portion of a blocked isocyanate are also well-known in the art. Examples of such suitable groups include: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols and amines. Of these, oximes (e.g., acetone oxime, methyl ethyl ketoxime, methyl amyl ketoxime, diisobutyl ketoxime, formaldehyde oxime) are preferred.
In a preferred embodiment of the present invention, the film-forming composition contains a catalyst to accelerate the cure of the polyisocyanate and other -crosslinkable groups. Examples of useful catalysts include: metal acetonyl acetates, quaternary ammonium salts, zinc N-ethyl-N-phenyl dithiocarbamate, pentamethyl-diethylenetriamine benzoate, cyclohexylamine acetate, n,n-dimethyl cyclohexylamine acetate, ketimines, N-methyl morpholine, tin octoate, stannic chloride, butyl tin trichloride, dibutyl tin diacetate, dibutyl tin dilaurate, bis(2-ethylhexyl) tin oxide, 1,3-diacetoxy tetrabutyl stannoxate, dibutyl dibutoxy tin, lead naphthenate, bismuth trichloride, bismuth octoate, tetrabis (2-ethylhexyl)titanate, tetrabutoxy titanium, stannous octoate, manganese, zirconium, cobalt, lead, bismuth stannate, lead stannate, zirconium octoate, tin, dibutyl tin maleate, stannous oxalate, stannous stearate, barium nitrate, zinc nitrate, dibutyltin dilauryl mercaptide, bismuth stearate, lead stearate, dimethyltin dichloride, stannous naphthate, dibutyltin bis-O-phenylphenate, dibutyltin S,S-dibutyldithio-carbonate, and triphenylantimony dichloride. Organometallic catalysts having tin as the metal are preferred. Of these, dibutyltin dilaurate is most preferred.
If employed, the catalyst is usually present in an amount ranging from between about 0.1 to about 5 weight percent, and preferably, from between about 0.5 to about 2 weight percent. These weight percentages are based upon the total weight of the resin solids in the coating composition.
In addition to the above, optional ingredients, such as plasticizers, flow controllers, anti-oxidants, UV light absorbers and other similar additives known in the art, can also be included in the coating composition. If employed, the cumulative weight of these optional ingredients are typically present at up to about 25 weight percent. This weight percentage is based upon the total weight of the resin solids in the coating composition.
The crosslinkable film-forming coating composition of the present invention can be used as the clear top coat layer in a "color-plus-clear" coating system. The base coat in a color-plus-clear system encompassed by the present invention can be any of the compositions useful in coatings applications, particularly those in automotive and general industrial applications. The film-forming composition of the base coat typically includes a resinous binder and a pigment. Examples of particularly useful resinous binders include acrylic polymers, polyesters (including alkyds) and polyurethanes.
The base coat compositions may be solvent-borne or water-borne. Examples of water-borne base coats in a color-plus-clear system encompassed by the present invention are disclosed in U.S. Pat. No. 4,403,003. Moreover, water-borne polyurethanes, such as those disclosed in U.S. Pat. No. 4,147,679, can also be used as the resinous binder in the base coat to prepare a coating-plus-clear system which is encompassed by the present invention. Further, water-borne coatings, such as those described in U.S. Pat. No. 5,071,904, can also be used as a base coat.
Base coats also often contain pigments in order to give them the desired color. Moreover, base coat compositions containing metallic flake pigmentation are often used in the production of so-called "glamour metallic" finishes. These types of finishes are mainly used in the automotive industry. Examples of metallic flakes which can be used in a base coat of a color-plus-clear system encompassed by this invention include: aluminum flake, copper bronze flake and metal oxide coated mica.
Besides the metallic pigments, the base coat compositions may also contain non-metallic color pigments conventionally used in surface coatings. Examples of such pigments include: inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green.
In general, non-metallic pigments are typically incorporated into the base coat composition in an amount ranging from between about 1 to about 80 percent by weight based on the total weight of coating solids. On the other hand, metallic pigments are typically employed in an amount ranging from between about 0.5 to 25 percent by weight based on the total weight of coating solids.
If desired, the base coat composition may contain additional materials well known in the art of formulated surface coatings. Examples of such additional materials include: surfactants, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts, and other customary auxiliaries. If employed, the cumulative weight of these materials can constitute up to 40 percent by weight of the total weight of the coating composition.
The base coat compositions of a color-plus-clear system encompassed by the present invention can be applied to various substrates such as metals, plastics, wood, glass, woven fibers, non-woven fibers, foams, or a combination thereof. They are, however, particularly useful when applied over metals and elastomeric substrates that are found on motor vehicles.
Moreover, the base coat compositions can be applied over such substrates by conventional means including brushing, dipping, flow coating, spraying and the like. Most often, the base coat composition is applied by spraying. Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used.
During application of the base coat composition to the substrate, a film of the base coat is formed on the substrate. Typically, the base coat thickness ranges from between about 0.01 to about 10 mils, and preferably, from between about 0.05 to about 5 mils, and even more preferably, from between about 0.1 to about 2 mils.
After application of the base coat to the substrate, a film is formed on the surface of the substrate by driving solvent out of the base coat by heating or by an air drying period. Preferably, the drying period is only for that time which is sufficient to ensure that the clear top coat can be applied over the base coat without the top coat dissolving the base coat. Suitable drying conditions will depend, in part, upon the particular base coat composition, the ambient humidity, and the like. In general, a drying time of from about 1 to about 5 minutes, at a temperature of about 68°-250° F. (20°-121° C.), will be adequate to ensure that mixing or "soak-in" of the two coats is minimized. At the same time, however, the base coat film is adequately wetted by the clear top coat composition so that satisfactory intercoat adhesion is obtained.
More than one base coat and/or top coat may be applied to develop the optimum appearance of a color-plus-clear system encompassed by the present invention. Usually, the previously applied coat is flashed (i.e., exposed to ambient conditions for about 1 to 20 minutes) between coats.
The clear top coat composition can be applied over the base coat film by any conventional coating technique. Examples of such conventional techniques include: brushing, dipping, flow coating, spraying and the like. Most often, the top coat is applied by spraying. Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used.
After application of the top coat over the base coat, the coated substrate is heated to cure the coating layers. In the curing operation, solvents are driven off and the film-forming materials of the clear coat and the base coat are each crosslinked. The heating or curing operation is usually carried out at a temperature of about 160°-350° F. (71°-177° C.). If needed, however, lower or higher temperatures may be used as necessary to activate crosslinking mechanisms. The thickness of the clear coat layer usually ranges from between about 0.1 to about 10 mils, preferably, from between about 0.5 to about 7 mils, and even more preferably, from between about 1 to about 5 mils.
The examples which follow are intended to assist in a further understanding of this invention. Particular materials employed, species and conditions are intended to be illustrative of specific embodiments of the invention.
The following initial charge and feeds were used in the preparation of cyclohexyl methacrylate containing acrylic resin by solution polymerization technique in xylene.
______________________________________
Ingredients Parts by Weight
______________________________________
Initial Charge
Xylene 540.0
Feed A
Cyclohexyl methacrylate
1559.4
2-Hydroxybutyl acrylate
240.6
Feed B
Xylene 540.0
VAZO ® 67.sup.1
90.0
______________________________________
.sup.1 2,2azobis (2methylbutanenitrile), available from E. I. du Pont
deNemours and Company.
The initial charge was heated in a reaction vessel with agitation to reflux temperature (138° C.). At reflux Feeds A and B were initiated simultaneously and continued in a substantially continuous manner over a period of 3 hours while maintaining the reaction mixture at reflux temperature. At the completion of Feeds A and B, the reaction mixture was held for 2 hours at reflux temperature to complete the polymerization. The reaction mixture was cooled and filtered. The resultant acrylic resin had a total solids content of 61.0 percent determined at 110° C. for one hour and number average molecular weight (Mn) of 2074 as determined by gel permeation chromatography (GPC) using polystyrene as standard. The resin had a Gardner-Holdt viscosity measured at 25° C. of P+.
The free radical addition polymers containing various amount of cyclohexyl methacrylate and hydroxyl functional monomers were prepared similar to Example 1 and their composition, solvent, solids content, Gardner-Holdt viscosity and number average molecular weight are tabulated in Table I.
TABLE I
__________________________________________________________________________
Ingredients
1 2 3 4 5 6 7 8 9 10 11 12
__________________________________________________________________________
CHMA.sup.1
1559.4
433.2
559.9
559.9
1800.0
552.0
540.0
1055.2
396.0
263.9
198.0
132.0
2-HBA.sup.2
240.6
66.8
40.1
40.1
600.0
-- -- -- -- -- -- --
2-HPA.sup.3
-- -- -- -- -- 48.0
60.0
144.8
72.3
72.3
72.3
72.3
MMA.sup.4
-- -- -- -- -- -- -- -- 65.9
131.9
164.9
197.9
n-BA.sup.5
-- -- -- -- -- -- -- -- 65.9
131.9
164.8
197.8
67ZO ®
90.0
25.0
30.0
30.0
120.0
30.0
30.0
60.0
30.0
30.0
30.0
30.0
Solvent.sup.6
XYL EtAc
XYL
EtAc
XYL XYL
XYL
XYL XYL
XYL
XYL
XYL
Solids (%)
61.0
52.0
58.1
66.7
63.0
62.4
61.1
62.3
60.9
58.2
64.2
57.7
Viscosity.sup.7
P+ R I Z6+
O+ U- R- T N I+ Q F
Mn 2074
7471
1574
7788
2035
2197
2737
1910
2311
2322
2696
2397
__________________________________________________________________________
.sup.1 Cyclohexyl methacrylate
.sup.2 2Hydroxybutyl acrylate
.sup.3 2Hydroxypropyl acrylate
.sup.4 Methyl methacrylate
.sup.5 nButyl acrylate
.sup.6 XYL: xylene; EtAc:ethyl acetate
.sup.7 GardnerHoldt at 25° C.
For the purpose of comparing the properties of compositions which contain cyclohexyl methacrylate with those that do not, a hydroxy functional polymer was prepared in accordance with Example II.1 of U.S. Pat. No. 4,565,730. That polymer was prepared as follows:
______________________________________
Ingredients Parts by Weight
______________________________________
Initial Charge
100.sup.1® 600.0
Feed A
n-Butyl acrylate 300.0
Ethyl acrylate 320.0
2-Hydroxypropyl acrylate
320.0
Acrylic acid 10.0
Styrene 50.0
Feed B
100MATIC ® 65.0
Di-tert-butyl peroxide
48.0
______________________________________
.sup.1 Aromatic hydrocarbon blend, available from Exxon Chemical Company.
The initial charge was heated in a reaction vessel with agitation to reflux temperature (163° C.). At reflux, Feeds A and B were initiated simultaneously and continued in a substantially continuous manner. The monomer mixture (Feed A) was added over a period of 4 hours and the initiator solution (Feed B) was added over 4.5 hours while maintaining the reaction mixture at reflux temperature. At the completion of Feeds A and B, the reaction mixture was held for 1 hour at reflux temperature to complete the polymerization. The reaction mixture was cooled and filtered. The resultant acrylic resin had a total solids content of 61.9 percent determined at 110° C. for one hour and number average molecular weight of 2092 as determined by gel permeation chromatography using polystyrene as a standard. The resin had a Gardner-Holdt viscosity measured at 25° C. of I-.
For the purpose of comparison, a hydroxy functional polymer was prepared in accordance with Example III.1 of U.S. Pat. No. 4,565,730. That polymer was prepared as follows:
______________________________________
Ingredients Parts by Weight
______________________________________
Initial Charge
Xylene 300.0
n-Butyl acetate 300.0
Feed A
2-Ethylhexyl methacrylate
150.0
Methyl methacrylate
345.0
Hydroxyethyl methacrylate
100.0
2-Hydroxypropyl methacrylate
150.0
Methacrylic acid 5.0
n-Butyl acrylate 100.0
Styrene 150.0
Feed B
Xylene 65.0
Di-tert-butyl peroxide
48.0
______________________________________
The initial charge was heated in a reaction vessel with agitation to reflux temperature (131° C.). At reflux, Feeds A and B were initiated simultaneously and continued in a substantially continuous manner. The monomer mixture (Feed A) was added over a period of 4 hours and the initiator solution (Feed B) was added over 4.5 hours while maintaining the reaction mixture at reflux temperature. At the completion of Feeds A and B, the reaction mixture was held for 1 hour at reflux temperature to complete the polymerization. The reaction mixture was cooled and filtered. The resultant acrylic resin had a total solids content of 60.8 percent determined at 110° C. for one hour and number average molecular weight of 12787 as determined by gel permeation chromatography using polystyrene as a standard. The resin had a Gardner-Holdt viscosity measured at 25° C. of Z7-.
A pigmented black base coating composition was used which is a high-solids polyester base coating composition available from PPG Industries, Inc. as POLYCRON® III base coat.
A clear film forming composition was formulated from the following ingredients:
______________________________________
Ingredients Parts by Weight
Solids
______________________________________
Acrylic resin of Example 1
229.78 140.17
DESMODUR ® BL 3175A.sup.1
52.98 39.74
Xylene 12.49 --
n-Butyl acetate 12.49 --
n-Butanol 6.25 --
TINUVIN ® 328.sup.2
14.28 4.28
TINUVIN ® 292.sup.3
2.25 1.11
Dibutyltin dilaurate
0.93 0.93
______________________________________
.sup.1 Methyl ethyl ketoxime blocked 1,6hexamethylene diisocyanate
available from BAYER Corp. in AROMATIC 100 available from Exxon Chemical
Company.
.sup.2 2(2Hydroxy-3',5ditert-amylphenyl) benzotriazoale UV light
stabilizer available from Ciba Geigy Corp. (dissolved in xylene).
.sup.3 Bis(1,2,2,6,6pentamethyl-4-piperidinyl) sebacate hindered amine
stabilizer available from Ciba Geigy Corp. (dissolved in isobutanol after
neutralization with dodecylbenzene sulfonic acid).
The clear coating compositions containing copolymers of cyclohexyl methacrylate and hydroxyl functional monomers were formulated similar to Example 16 and their compositions in solid grams are tabulated in Table II.
TABLE II
__________________________________________________________________________
Ingredients
16 17 18 19 20 21 22 23 24 25 26 27
__________________________________________________________________________
DESMODUR ®
39.74
37.57
21.28
20.99
62.85
27.55
34.42
39.31
39.66
38.19
39.71
40.14
BL 3175 A
Resin from Example 1
140.17
-- -- -- -- -- -- -- -- -- -- --
Resin from Example 2
-- 132.57
-- -- -- -- -- -- -- -- --
Resin from Example 3
-- -- 150.29
-- -- -- -- -- -- -- -- --
Resin from Example 4
-- -- -- 148.21
-- -- -- -- -- -- -- --
Resin from Example 5
-- -- -- -- 118.79
-- -- -- -- -- -- --
Resin from Example 6
-- -- -- -- -- 146.50
-- -- -- -- -- --
Resin from Example 7
-- -- -- -- -- -- 146.20
-- -- -- -- --
Resin from Example 8
-- -- -- -- -- -- -- 138.67
-- -- -- --
Resin from Example 9
-- -- -- -- -- -- -- -- 139.87
-- -- --
Resin from Example 10
-- -- -- -- -- -- -- -- -- 134.73
--
Resin from Example 11
-- -- -- -- -- -- -- -- -- -- 140.04
--
Resin from Example 12
-- -- -- -- -- -- -- -- -- -- -- 141.57
TINUVIN ® 328
4.28 4.05
4.09
4.04 4.32
4.15
4.30 4.24
4.28
4.12 4.28
4.33
TINUVIN ® 292
1.11 1.06
1.06
1.05 1.12
1.08
1.12 1.11
1.11
1.08 1.12
1.12
Dibutyltin dilaurate
0.93 0.88
0.88
0.88 0.93
0.90
0.94 0.92
0.93
0.89 0.93
0.94
__________________________________________________________________________
Comparative clear coating compositions containing DESMODUR® BL 3175A and hydroxyl functional polymers were formulated similar to Examples 16-27 using Comparative Examples 13-14 and commercially available fluorinated polyols. Their compositions in grams of resin solids are tabulated in Table III.
TABLE III
______________________________________
INGREDIENTS 28 29 30 31 32
______________________________________
DESMODUR ® BL
75.06 77.39 79.71 46.34 70.58
3175A
Resin from Example 13
57.47 78.32 98.14 -- --
Resin from Example 14
57.47 33.55 10.91 -- --
LUMIFLON ® LF200.sup.1
-- -- -- 163.57 --
LUMIFLON ® LF916.sup.2
-- -- -- -- 144.34
TINUVIN ® 328
4.48 4.47 4.47 4.91 5.11
TINUVIN ® 292
1.15 1.23 1.20 1.37 1.33
Dibutyltin dilaurate
0.80 0.78 0.76 0.82 0.88
______________________________________
.sup.1 Fluoropolymer with hydroxyl number of 52 available from Asahi Glas
Company, Ltd., Japan.
.sup.2 Fluoropolymer with hydroxyl number of 90 available from Asahi Glas
Company, Ltd., Japan.
The base coating composition prepared according to Example 15 was air-atomized spray applied to pretreated aluminum panels at room temperature to attain a dry film thickness of 0.8 to 1.2 mils. After a 10 minute flash, the panels were then baked for 10 minutes at 350° F. (177° C.). The panels were allowed to cool room temperature and the prepared clear coating compositions were applied to the base coating. The clear coatings of Examples 16 to 27 and Comparative Examples 28 to 32 were applied in four successive coats at room temperature with film ranges from 1.8 to 2.2 mils. Each panel was given a 10 minute flash at room temperature, 10 minute "force" flash at 150° F. (66° C.), and then baked for 30 minutes at 285° F. (141° C.).
The films were then evaluated for durability and acid etch resistance. The durability tests were done using Xenon arc Weather-Ometer with quartz/borosilicate filter combination from 340 nm. The cycle was: 40 minutes light; 20 minutes light with specimen spray; 60 minutes light; 60 minutes dark cycle with both specimen and rack spray. The results after 2000 hours exposure are tabulated in Table IV. The acid etch resistance of the films were evaluated via a 3-cycle sulfurous acid spray test. The acid solution with pH of 2 was prepared by adding 12 grains of H2 SO3 to 350 grams of deionized water. The test consists of misting 3"×5" panel sections with the acid solution to completely cover the panels densely with droplets and then placing the panels in a 120° F. (49° C.) oven for 20 minutes. This constitutes one cycle. The procedure is then repeated two times. The panels are then washed with soap and water and towel dried for evaluation. The acid etch results are reported in Table IV.
Table IV
__________________________________________________________________________
Calculated
2000 HOURS WEATHER-OMETER
Clear
% CHMA
OH Number
Initial
% Gloss Acid
Coat Content
on Solids
Gloss
Retention.sup.2
Remarks Etch.sup.3
__________________________________________________________________________
EX. 16
86.6 52 89 98 No Spotting or etching
9
EX. 17
86.6 52 90 99 Slight Spotting, no etching
10
EX. 18
93.3 26 91 96 Etched, Slight Spotting
8
EX. 19
93.3 26 89 94 Etched 10
EX. 20
75 97.4 91 96 Slight Spotting, no etching
10
EX. 21
92 34.5 88 94 Slight Spotting, no etching
10
EX. 22
90 43.2 90 97 No Spotting, no etching
10
EX. 23
87.9 52 89 98 Slight Spotting, no etching
_ 9
EX. 24
66 52 91 96 Slight Spotting, no etching
7-8
EX. 25
44 52 89 85 Spotting, no etching
7
EX. 26
33 52 88 78 Spotting, no etching
8
EX. 27
22 52 88 61 Spotting, no etching
4-5
EX.28
0 12O 91 85 Spotting, no etching
4-5
EX. 29
0 129 91 70 Spotting, no etching
4
EX. 30
0 134 88 76 Spotting, no etching
3-4
EX. 31
0 52 83 96 No Spotting or etching
10
EX. 32
0 90 87 92 No Spotting or etching
9
__________________________________________________________________________
.sup.1 Measured with a GLOSSGARD ® RII glossmeter at 60°.
.sup.2 Measured finaI gloss/measured initial gIoss multiolied by 1OO.
.sup.3 Rating scale: 10 = no acid etch and 0 = severe acid etch.
It is evident from the foregoing that various modifications, which are apparent to those skilled in the art, can be made to the embodiments of this invention without departing from the spirit or scope thereof. Having thus described the invention, it is claimed as follows.
Claims (20)
1. A film-forming coating composition comprising:
(a) a hydroxyl-containing acrylic solution polymer which is the polymerization product of monomeric components consisting of:
(i) a first monomeric component employed in an amount ranging from about 45 to about 95 weight percent, said weight percentages being based upon the total weight of all monomers used in preparing the hydroxyl-containing acrylic solution polymer, said first monomeric component is at least one compound selected from the group consisting of:
a. cycloaliphatic esters of (meth)acrylic acid selected from the group consisting of t-butyl-cyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate, and
b. aromatic esters of (meth)acrylic acid, and
(ii) a second monomeric component which consists of at least one hydroxyl functional acrylic monomer present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60, and
(b) a polyisocyanate crosslinking agent.
2. The composition of claim 1 wherein the first monomeric component consists of cyclohexyl methacrylate or a mixture of cyclohexyl methacrylate and at least one compound selected from the group consisting of: t-butyl-cyclohexyl(meth)acrylate, cyclohexyl acrylate and aromatic esters of (meth)acrylic acid.
3. The composition of claim 1 wherein the acrylic solution polymer has a hydroxyl number ranging from between about 25 to about 55.
4. The composition of claim 1 wherein the polyisocyanate crosslinking agent is present in an amount ranging from between about 10 to about 40 percent by weight, based on the total weight of resin solids.
5. The composition of claim 1 wherein said at least one hydroxyl functional acrylic monomer consists of at least one compound selected from the group consisting of: 2-hydroxybutyl acrylate and 2-hydroxypropyl acrylate.
6. The composition of claim 1 wherein the acrylic solution polymer has a number average molecular weight of 1,500 to 20,000.
7. The composition of claim 1 wherein the polyisocyanate crosslinking agent is blocked.
8. The composition of claim 1 wherein the first monomeric component consists of t-butyl-cyclohexyl (meth)acrylate or a mixture of t-butyl-cyclohexyl(meth)acrylate and at least one compound selected from the group consisting of: cyclohexyl(meth)acrylate and aromatic esters of (meth)acrylic acid.
9. The composition of claim 5 wherein said at least one hydroxyl functional acrylic monomer consists of 2-hydroxybutyl acrylate.
10. A film-forming coating composition comprising:
(a) a hydroxyl-containing acrylic solution polymer which is the polymerization product of monomeric components consisting of:
(i) a first monomeric component employed in an amount ranging from about 45 to about 95 weight percent, said weight percentages being based upon the total weight of all monomers used in preparing the hydroxyl-containing acrylic solution polymer, said first monomeric component is at least one compound selected from the group consisting of:
a. cycloaliphatic esters of (meth)acrylic acid selected from the group consisting of t-butyl-cyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate, and
b. aromatic esters of (meth)acrylic acid,
(ii) a second monomeric component employed in an amount up to about 45 weight percent, said weight percentage being based upon the total weight of all monomers used in preparing the hydroxyl-containing acrylic solution polymer, said second monomeric component is at least one compound selected from the group consisting of: vinyl aromatic compounds, and alkyl (meth)acrylates containing from 1 to 8 carbon atoms in the alkyl group, and
(iii) a third monomeric component which consists of at least one hydroxyl functional acrylic monomer present in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than 60, and
(b) a polyisocyanate crosslinking agent.
11. The composition of claim 10 wherein the first monomeric component consists of cyclohexyl methacrylate or a mixture of cyclohexyl methacrylate and at least one compound selected from the group consisting of: t-butyl-cyclohexyl(meth)acrylate, cyclohexyl acrylate and aromatic esters of (meth)acrylic acid.
12. The composition of claim 10 wherein the acrylic solution polymer has a hydroxyl number ranging from between about 25 to about 55.
13. The composition of claim 10 wherein the polyisocyanate crosslinking agent is present in an amount ranging from between about 10 to about 40 percent by weight, based on the total weight of resin solids.
14. The composition of claim 10 wherein said at least one hydroxyl functional acrylic monomer consists of at least one compound selected from the group consisting of: 2-hydroxybutyl acrylate and 2-hydroxypropyl acrylate.
15. The composition of claim 10 wherein the acrylic solution polymer has a number average molecular weight of 1,500 to 20,000.
16. The composition of claim 10 wherein the polyisocyanate crosslinking agent is blocked.
17. The composition of claim 10 wherein the second monomeric component is at least one vinyl aromatic compound, and wherein said at least one vinyl aromatic compound consists of selected from the group consisting of styrene and vinyl toluene.
18. The composition of claim 17 wherein the second monomeric component consists of styrene.
19. The composition of claim 10 wherein the second monomeric component consists of at least one alkyl (meth)acrylate containing from 1 to 8 carbon atoms in the alkyl group, and wherein said at least one alkyl (meth)acrylate consists of selected from the group consisting of: methyl methacrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate and 2-ethylhexyl acrylate.
20. The composition of claim 19 wherein the second monomeric component consists of a mixture of n-butyl (meth)acrylate and methyl methacrylate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/574,825 US5849835A (en) | 1995-12-19 | 1995-12-19 | Polyisocyanate cured ultradurable glossy coating compositions |
| PCT/US1996/017595 WO1997022645A1 (en) | 1995-12-19 | 1996-11-04 | Polyisocyanate cured ultradurable glossy coating compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/574,825 US5849835A (en) | 1995-12-19 | 1995-12-19 | Polyisocyanate cured ultradurable glossy coating compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5849835A true US5849835A (en) | 1998-12-15 |
Family
ID=24297810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/574,825 Expired - Fee Related US5849835A (en) | 1995-12-19 | 1995-12-19 | Polyisocyanate cured ultradurable glossy coating compositions |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5849835A (en) |
| WO (1) | WO1997022645A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6045872A (en) * | 1998-05-01 | 2000-04-04 | Basf Corporation | Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein |
| US6054248A (en) * | 1999-03-12 | 2000-04-25 | Arch Specialty Chemicals, Inc. | Hydroxy-diisocyanate thermally cured undercoat for 193 nm lithography |
| US6432543B2 (en) * | 1998-07-29 | 2002-08-13 | Basf Corporation | Decorative components having an elastomeric outer surface and methods of making such components |
| US20030212217A1 (en) * | 2002-05-08 | 2003-11-13 | Suresh Sawant | Fluorinated activator |
| US20060147639A1 (en) * | 2004-12-22 | 2006-07-06 | Nippon Paint Co., Ltd. | Clear coating composition for an automobile and method of forming a multi-layer coating film using the same |
| US8460795B2 (en) | 2007-04-12 | 2013-06-11 | Ppg Industries Ohio, Inc. | Curable film-forming compositions demonstrating burnish resistance and low gloss |
| US9080004B2 (en) | 2010-10-07 | 2015-07-14 | Prc-Desoto International, Inc. | Diethylene glycol monomethyl ether resistant coating |
| US10370555B2 (en) | 2017-05-16 | 2019-08-06 | Ppg Industries Ohio, Inc. | Curable film-forming compositions containing hydroxyl functional acrylic polymers and bisurea compounds and multilayer composite coatings |
| US10597550B2 (en) | 2015-11-24 | 2020-03-24 | Dow Global Technologies Llc | Aqueous polymer dispersion and process of making the same |
| US10934449B2 (en) | 2016-07-29 | 2021-03-02 | Behr Process Corporation | Water based sealer with superior durability |
| US11591464B2 (en) | 2017-07-14 | 2023-02-28 | Ppg Industries Ohio, Inc. | Curable film-forming compositions containing reactive functional polymers and polysiloxane resins, multilayer composite coatings, and methods for their use |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345057A (en) * | 1980-08-08 | 1982-08-17 | Asahi Glass Company, Ltd. | Curable fluorocopolymer |
| JPS5817174A (en) * | 1981-07-23 | 1983-02-01 | Dainippon Ink & Chem Inc | Resin composition for coating |
| US4565730A (en) * | 1983-06-18 | 1986-01-21 | Basf Farben & Fasern Ag | Coating composition, in particular for producing a transparent topcoat of a multilayer coating, a process for producing coatings, and an article coated with a multilayer coating |
| JPS63142009A (en) * | 1986-12-05 | 1988-06-14 | Nippon Shokubai Kagaku Kogyo Co Ltd | Acrylpolyol and two-pack urethane resin coating composition containing same |
| EP0337744A2 (en) * | 1988-04-12 | 1989-10-18 | Nippon Shokubai Co., Ltd. | Ultraviolet-stable copolymer. Process for producing the same, and coating composition containing the same |
| US5279862A (en) * | 1991-10-21 | 1994-01-18 | E. I. Du Pont De Nemours And Company | Process for refinishing clear coat/color coat finish |
| WO1994009916A1 (en) * | 1992-11-04 | 1994-05-11 | Basf Lacke + Farben Aktiengesellschaft | Method for forming a paint film and coating obtained by the method |
| WO1994022969A1 (en) * | 1993-03-31 | 1994-10-13 | Basf Lacke + Farben Ag | Process for applying a double-layered covering lacquer on the surface of a substrate |
| US5445850A (en) * | 1994-02-18 | 1995-08-29 | Ppg Industries, Inc. | Aminoplast cured acid etch resistant coating with good durability |
| DE4407415A1 (en) * | 1994-03-05 | 1995-09-07 | Basf Lacke & Farben | Coating compositions based on a hydroxyl-containing polyacrylate resin and its use in processes for producing a multicoat paint system |
| EP0676423A1 (en) * | 1994-04-06 | 1995-10-11 | Imperial Chemical Industries Plc | Polymer |
-
1995
- 1995-12-19 US US08/574,825 patent/US5849835A/en not_active Expired - Fee Related
-
1996
- 1996-11-04 WO PCT/US1996/017595 patent/WO1997022645A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345057A (en) * | 1980-08-08 | 1982-08-17 | Asahi Glass Company, Ltd. | Curable fluorocopolymer |
| JPS5817174A (en) * | 1981-07-23 | 1983-02-01 | Dainippon Ink & Chem Inc | Resin composition for coating |
| US4565730A (en) * | 1983-06-18 | 1986-01-21 | Basf Farben & Fasern Ag | Coating composition, in particular for producing a transparent topcoat of a multilayer coating, a process for producing coatings, and an article coated with a multilayer coating |
| JPS63142009A (en) * | 1986-12-05 | 1988-06-14 | Nippon Shokubai Kagaku Kogyo Co Ltd | Acrylpolyol and two-pack urethane resin coating composition containing same |
| EP0337744A2 (en) * | 1988-04-12 | 1989-10-18 | Nippon Shokubai Co., Ltd. | Ultraviolet-stable copolymer. Process for producing the same, and coating composition containing the same |
| US5279862A (en) * | 1991-10-21 | 1994-01-18 | E. I. Du Pont De Nemours And Company | Process for refinishing clear coat/color coat finish |
| WO1994009916A1 (en) * | 1992-11-04 | 1994-05-11 | Basf Lacke + Farben Aktiengesellschaft | Method for forming a paint film and coating obtained by the method |
| WO1994022969A1 (en) * | 1993-03-31 | 1994-10-13 | Basf Lacke + Farben Ag | Process for applying a double-layered covering lacquer on the surface of a substrate |
| US5445850A (en) * | 1994-02-18 | 1995-08-29 | Ppg Industries, Inc. | Aminoplast cured acid etch resistant coating with good durability |
| DE4407415A1 (en) * | 1994-03-05 | 1995-09-07 | Basf Lacke & Farben | Coating compositions based on a hydroxyl-containing polyacrylate resin and its use in processes for producing a multicoat paint system |
| EP0676423A1 (en) * | 1994-04-06 | 1995-10-11 | Imperial Chemical Industries Plc | Polymer |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6045872A (en) * | 1998-05-01 | 2000-04-04 | Basf Corporation | Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein |
| US6432543B2 (en) * | 1998-07-29 | 2002-08-13 | Basf Corporation | Decorative components having an elastomeric outer surface and methods of making such components |
| US6649107B2 (en) | 1998-07-29 | 2003-11-18 | Basf Corporation | Decorative components having an elastomeric outer surface and methods of making such components |
| US20040058165A1 (en) * | 1998-07-29 | 2004-03-25 | Harrison Richard P. | Decorative components having an elastomeric outer surface and methods of making such components |
| US6852403B2 (en) | 1998-07-29 | 2005-02-08 | Basf Corporation | Decorative components having an elastomeric outer surface and methods of making such components |
| US6054248A (en) * | 1999-03-12 | 2000-04-25 | Arch Specialty Chemicals, Inc. | Hydroxy-diisocyanate thermally cured undercoat for 193 nm lithography |
| US20030212217A1 (en) * | 2002-05-08 | 2003-11-13 | Suresh Sawant | Fluorinated activator |
| US8138258B2 (en) * | 2004-12-22 | 2012-03-20 | Nippon Paint Co., Ltd. | Clear coating composition for an automobile and method of forming a multi-layer coating film using the same |
| US20060147639A1 (en) * | 2004-12-22 | 2006-07-06 | Nippon Paint Co., Ltd. | Clear coating composition for an automobile and method of forming a multi-layer coating film using the same |
| US8460795B2 (en) | 2007-04-12 | 2013-06-11 | Ppg Industries Ohio, Inc. | Curable film-forming compositions demonstrating burnish resistance and low gloss |
| US9080004B2 (en) | 2010-10-07 | 2015-07-14 | Prc-Desoto International, Inc. | Diethylene glycol monomethyl ether resistant coating |
| US10597550B2 (en) | 2015-11-24 | 2020-03-24 | Dow Global Technologies Llc | Aqueous polymer dispersion and process of making the same |
| US10934449B2 (en) | 2016-07-29 | 2021-03-02 | Behr Process Corporation | Water based sealer with superior durability |
| US11572487B2 (en) | 2016-07-29 | 2023-02-07 | Behr Process Corporation | Water based sealer with superior durability |
| US10370555B2 (en) | 2017-05-16 | 2019-08-06 | Ppg Industries Ohio, Inc. | Curable film-forming compositions containing hydroxyl functional acrylic polymers and bisurea compounds and multilayer composite coatings |
| US11591464B2 (en) | 2017-07-14 | 2023-02-28 | Ppg Industries Ohio, Inc. | Curable film-forming compositions containing reactive functional polymers and polysiloxane resins, multilayer composite coatings, and methods for their use |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997022645A1 (en) | 1997-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5663233A (en) | Coating agents and the use thereof in processes for the production of multi-layer coatings | |
| US6458885B1 (en) | Fast drying clear coat composition | |
| JP2001501986A (en) | High solids and powder coatings with hydroxy-functional acrylic resins | |
| WO1995022582A1 (en) | Aminoplast cured acrylic coating | |
| US5849835A (en) | Polyisocyanate cured ultradurable glossy coating compositions | |
| CA2146479C (en) | Polymer | |
| JPH07286138A (en) | Coating composition | |
| US20140329934A1 (en) | Coating composition | |
| JPH0753917A (en) | Coating material and its use especially in producing transparent or pigmented topcoating material | |
| JP4230537B2 (en) | Scratch resistant coating composition | |
| JPH0319271B2 (en) | ||
| CA1093238A (en) | Coating binder compositions comprising reactive hydroxyl-containing acrylic polymers | |
| EP1454934B1 (en) | Two-component coating compositions | |
| US5612415A (en) | Process for coating a substrate with coatings including high Tg acrylic polymers and coated article obtained thereby | |
| WO1997022646A1 (en) | Polyisocyanate cured ultradurable glossy coating compositions | |
| EP1541647A1 (en) | Aqueous two-component coating compositions | |
| EP1211267B1 (en) | Coating compositions based on hydroxy-functional (meth)acrylic copolymers | |
| JP4296178B2 (en) | Coating composition and coated product formed by coating the same | |
| AU2007241111B2 (en) | Adhesion-promoting compositions and methods of promoting adhesion between a coating and a substrate | |
| CN112888566A (en) | Automobile parts | |
| US5658988A (en) | Resinous composition for coating | |
| CA1102037A (en) | Block polymers of acrylic segments and polymercaptan segments | |
| JP3163443B2 (en) | Resin composition for paint | |
| JPH0418964A (en) | Method for coating reactive injection-molded product | |
| CA2258855C (en) | High-solids and powder coatings from hydroxy-functional acrylic resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: PPG INDUSTRIES, INC., PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DAS, SURYYA K.;KILIC, SONER;LAUER, ANDREW J.;REEL/FRAME:007954/0388 Effective date: 19960320 |
|
| AS | Assignment |
Owner name: PPG INDUSTRIES OHIO, INC., OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:PPG INDUSTRIES, INC.;REEL/FRAME:009737/0591 Effective date: 19990204 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| REMI | Maintenance fee reminder mailed | ||
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20101215 |
|
| AS | Assignment |
Owner name: PPG INDUSTRIES OHIO, INC., OHIO Free format text: CORRECTIVE ASSIGNMENT TO CORRECT INCORRECT PROPERTY NUMBERS 08/666726;08/942182;08/984387;08/990890;5645767;5698141;5723072;5744070;5753146;5783116;5808063;5811034 PREVIOUSLY RECORDED ON REEL 009737 FRAME 0591. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT;ASSIGNOR:PPG INDUSTRIES, INC.;REEL/FRAME:032513/0174 Effective date: 19990204 |